Insertion of CS(2) into iridium-fluorine bonds

Area of Science:

• Organometallic Chemistry
• Fluorine Chemistry
• Catalysis

Background:

• The formation of carbon-fluorine bonds is crucial in synthetic chemistry.
• Iridium complexes are versatile catalysts with unique reactivity.
• Understanding reaction mechanisms is key to developing new synthetic methods.

Purpose of the Study:

• To investigate the reaction of specific iridium fluorido complexes with carbon disulfide (CS2).
• To elucidate the mechanism of the observed carbon-fluorine bond formation.
• To explore the potential of CS2 as a reagent in organometallic transformations.

Main Methods:

• Synthesis of trans-[Ir(Ar(F))(F)(H)(PiPr3)2] complexes.
• Reaction of iridium complexes with carbon disulfide (CS2).
• Density Functional Theory (DFT) calculations to study the reaction mechanism.

Main Results:

• Formation of fluorodithiocarbonato species trans-[Ir(Ar(F))(H)(κ(2)-(S,S)-S2CF)(PiPr3)2].
• Observation of a novel C-F bond formation via CS2 insertion into the Ir-F bond.
• DFT studies suggest a concerted metathesis-like mechanism for C-F bond formation.

Conclusions:

• CS2 can effectively mediate C-F bond formation with iridium fluorido complexes.
• The reaction proceeds through an unprecedented concerted metathesis-like pathway.
• This finding opens new avenues for synthesizing fluorinated organometallic compounds.